Filterable surfactant composition

ABSTRACT

An improved aqueous soluble surfactant which has particular utility for incorporating in etchants for semiconductor devices is provided. The surfactant comprises a combination of a linear perfluorocarboxylic acid, a cyclic amine and an aliphatic alcohol.

This is a continuation-in-part application of application Ser. No. 10/984,649 filed Nov. 9, 2004, now U.S. Pat. No. 7,112,289.

This invention relates to a soluble surfactant capable of maintaining reduced surface tensions for increased wetting stability even after undergoing intense filtration. Surfactants with this capability have particular importance for use in integrated circuit manufacture. Specifically, this invention relates to a surfactant composition comprised of a three-component surfactant blend comprising a combination of a linear perfluorocarboxylic acid, a cyclic alkylamine and an aliphatic alcohol. The three-component surfactant system of the invention has been found to be highly effective when used in a variety of etchants including for example: ammonium fluoride-hydrofluoric acid (HF) blends; ammonium fluoride HF-phosphoric acid (PA) blends; PA-nitric acid-acetic acid blends; PA-nitric acid-acetic acid-fluoboric acid-HF blends; PA-nitric acid-sulfuric acid-HF blends; nitric acid-sulfuric acid—HF blends; nitric acid-HF-acetic acid and nitric acid-sulfuric acid blends.

BACKGROUND OF THE INVENTION

As integrated circuit component dimensions become smaller, physical wetting by etchant solutions on a substrate becomes more difficult. This is especially important for those buffered etchant solutions used in silicon dioxide etching, which in the absence of surfactants exhibit unacceptably high surface tension.

Due to the increasingly stringent requirements suitable silicon dioxide etchants must possess lower surface tension wherein the surfactant incorporated maintains an acceptable level of surface activity in hydrofluoric acid and ammonium fluoride etch systems.

Prior attempts have been made to produce stable aqueous solutions of surfactant containing ammonium fluoride and hydrofluoric acid etchants. For example, in U.S. Pat. No. 4,517,106 a fluoroalkylsulfonate is used to improve the wetting properties of the acid solutions. In U.S. Pat. No. 4,761,245 a nonionic alkylphenol polyglycidol is used for the same purpose.

In U.S. Pat. No. 4,795,582, it is disclosed that surfactants selected from the group consisting of aliphatic carboxylic acids and salts thereof, aliphatic amines and aliphatic alcohols are added to aqueous mixtures of ammonium fluoride and hydrofluoric acid to improve surface wetting. Among the various surfactant compounds, octylamine is disclosed in this patent as being suitable.

In U.S. Pat. No. 5,496,485 the patentee discloses the utilization of branched aliphatic amine surfactants. The addition of relatively substantial quantities of the surfactant, i.e., amounts in excess of 100 ppm based on the weight of etchants, are functionally required according to that patent.

The present invention provides the means to produce significantly improved surfactants which are superior from a practical standpoint of filterability, effectiveness and reduction of the surfactant quantity required.

In accordance with the invention, filtration of the surfactant must be conducted so as to reduce to a minimum the presence of particulates which may adversely affect the end use of semi-conductor components processed with compositions containing the surfactant.

In general, in pilot plant runs, integration of the surfactant into the etchant solution is effected by using a rotating mixer with a mixing period of the order of about 3 to 5 minutes. Also, in pilot plant runs, to assure a reasonable period for maximum removal of undesirable particulates from the surfactant containing etchant solution (water being the solvent unless otherwise indicated), a recirculating filtration process for a period of the order of at least about 12 hours is employed. The normal flow rate through the centrifugal pump associated with the recirculating filtration system is approximately one gallon per minute.

In commercial runs, i.e., in 100 lbs. to 3,000 lbs. batches, for example, a rotating mixer of a kind employed in the art is used to blend the surfactant into the etchant solution using a minimum blending period of approximately 3 to 5 minutes. The blend is then subjected to suitable multipass filtration operation that is continued until the desired minimum level or elimination of undesirable particulates is attained while still retaining a minimum but sufficient quantity of surfactant to provide the desired surface tension reduction in the etchant composition.

It is apparent that the quantity of surfactant retained in the etchant, for practical reasons, is the minimum amount that provides the suitable surface tension reduction. Generally, it is desired that a surfactant amount impart a functional level to the solution after the surfactant containing solution is filtered. For example, for etchants, an effective amount of surfactant retained in the filtered etchant may vary from about 10 ppm to about 100 ppm with about 35 to about 65 ppm (based on the weight of the etchant) being the more optimal quantities.

SUMMARY OF THE INVENTION

It is accordingly, an object of the present invention to provide surfactants that provide improved wetting properties compared to known prior art surfactants and which retain excellent surface active properties after filtration.

It is a further object of the invention to provide surfactants which, when incorporated in solutions and which after a filtration through medium of the order of 0.1 micron, yield a product which retains an effective level of surfactant and which provides better wetting characteristics and does not adversely affect the desired characteristics of the solution.

These and other objects of the invention are provided by the provision of a novel multi-component surfactant of the kind described above.

The criteria for the surfactant of the invention comprise chemical additives that provide:

-   -   1. Surface tension in etchants of less than or equal to 45         dynes/cm² and preferably a surface tension in etchants of less         than or equal to 25 dynes/cm²     -   2. Filterability that permits successful removal of sub-micron         particulates through multiple pass filtration to achieve:         -   10 counts maximum per ml at greater than or equal to 1.0             micron         -   100 counts maximum per ml at greater than or equal to 0.5             micron while retaining surfactant in etchant.     -   3. Trace metallic contribution from the surfactant to the         surfacted-treated solution is ≦10 ppb for all the common         metallic elements such as Al, Cr, Fe, Ca, Na, and Ni because         limits of this order are generally critical to the semiconductor         manufacturing process.     -   4. Insignificant foaming wherein the height of foam column         disappears in less than 5 minutes, or is invisible.

A suitable surfactant should meet the criteria described in above paragraphs 1-4.

Experiments incorporating these surfactants in etchant were carried out in pilot scale (1 lb. to 100 lbs. batches) as well as full-scale production of several batches of quantities up to 3,000 lbs. using surfactants of the kind described in accordance with the present invention. These experiments successfully demonstrated the superior effectiveness of the surfactants.

The surfactants of the invention are obtained by adding a tri-component system comprising solutions of concentrations between about 0.1% and 99% by weight of the compounds selected from those described hereinbelow as a, b, and c. The surfactant content, when used in etchants, comprises a small amount, i.e., on the order of at least about 10 ppm. The tri-component surface-active agent comprises a blend of (i) a cyclic amine, (ii) a straight chain perfluorocarboxylic acid, and (iii) an aliphatic alcohol.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the present invention, the novel surfactants comprise a blend of:

-   -   (i) an aliphatic cyclic amine of the formula         (CH₂)_(x−1)CHNH₂         -   wherein x has a value of 5-8;     -   (ii) a linear perfluorocarboxylic acid of the formula         C_(n−1)F_(2n−1)COOH         -   wherein n has a value of 4 to 11 and yields a perfluoramide             of the formula             C_(n−1)F_(2n−1)CONHCH(CH₂)_(x−1)         -   when reacted with the cyclic amine; and     -   (iii) an alcohol of the formula         C_(n)H_(2n+1)OH         -   wherein n is an integer from 1 to 5.

Although quantities of the above-described tri-component surfactant in amounts in excess of 10 ppm, i.e., even exceeding 100 ppm, may be incorporated to provide the desired effect, such greater amounts are unnecessary from a practical standpoint. Generally, an amount of surfactant between about 10 to about 100 ppm and preferably 15 ppm to 90 ppm is usually sufficient. We have found that when an etchant containing the surfactant of the invention is used in recirculation filtration tanks, the surfactant is retained in the etchant following the filtration. Use of the surfactant also, advantageously, does not give rise to significant foaming.

The invention will further be illustrated by reference to the following procedure and examples describing the preparation of the surfactants of the invention. In preparing the surfactants, the following reaction is applied:

wherein R is the fluorinated hydrocarbon chain of the perfluorocarboxylic acid, R′ is the cyclic hydrocarbon portion of the cyclic amine.

In the examples, a surfactant was added to a mixture of predetermined amounts of hydrofluoric acid, ammonium fluoride and deionized water to prepare an etchant composition. The prepared composition was kept standing at room temperature and test samples were periodically withdrawn to measure the change of surface tension of the composition.

An illustrative typical reaction of the perfluorocarboxylic acid and the cyclic amine of perfluorooctanoic acid and cycloheptylamine are cited as follows:

-   Preparation: 10% of surfactant as mixed in 50% by weight isopropyl     or 2-propanol (IPA) stock solution is prepared in accordance with     the reaction above using perfluorooctanoic acid and cycloheptyl     amine. Composition of 100 g of 10% surfactant include:

 5 g acid (approx. 99%)  5 g amine (approx. 99%) 45 g IPA (approx. 99%) 45 g H₂O

-   -   The acid and amine were pre-mixed at room temperature and heated         in a boiling water bath for at least 30 minutes to speed up and         to drive the reaction to completion and the resulting mixture         cooled to near room temperature (20-30° C.). The IPA and H₂O (or         a premix of IPA and H₂O) is then added.         The following is a typical example of Synthesis and Preparation         of the claimed Surfactants Reaction:

-   -   wherein R is the fluorinated hydrocarbon chain of the         perfluorocarboxylic acid, Ŕ is the cyclic hydrocarbon portion of         the cyclic amine, i.e., reaction of perfluorooctanoic acid and         cycloheptylamine

PREPARATORY EXAMPLE

An aqueous solution of 10% of surfactant in 50% 2-propanol (by weight)

-   -   i.e., refer to the reaction above of perfluorooctanoic acid and         cycloheptyl amine.     -   Composition of 100 g of 10% surfactant include:     -   5 g Acid (approx. 99% purity)     -   5 g Amine (approx. 99% purity)     -   45 g 2-propanol (approx. 99% purity)     -   45 g deionized H₂O

Various runs were conducted to demonstrate that the surfactant(s) met the desired criteria. Generally the experimental runs were carried out in pilot scale (1 lb. to 100 lbs. batches).

General Run

A preliminary testing was conducted prior to filtration to evaluate whether individual components of the claimed surfactant(s), would work individually, need modification, or require combining to give a basic understanding which would lead to synthesis of the surfactant(s) of the invention. Potential surfactant candidates were prepared and evaluated in an aqueous mixture comprised of about 35% by weight of ammonium fluoride, NH₄F., and about 6.3% by weight of hydrofluoric acid, HF, (defined as BOE 7-1). Dosages were varied and dependant on which surfactant was employed, incremental additions were performed, measurements of surface tension at 25° C. were made until surface tension stabilized or until the surfactant reached a saturation point (limit in solubility). The results are given in Table I below:

TABLE I Surface Tension Solubility Promising Potential Surfactants (dynes/cm²) In BOE Comments (Yes/No) A. Cycloheptylamine 72 ≦400 ppm ST too high No B. Cyclooctylamine 65 ≦600 ppm ST too high No C. Cyclopentylamine 65 ≦400 ppm ST too high No D. Perfluorooctanoic Acid 20 ≦100 ppm Precipitated No E. Perfluoroheptanoic Acid 20 ≦100 ppm Precipitated No F. Perfluorononanoic Acid 25 ≦100 ppm Precipitated No G. Perfluoropentanoic Acid 24 ≦100 ppm Precipitated No H. A + D 20 ≦1000 ppm  Good ST, Yes Fairly soluble I. B + D 20 ≦500 ppm Good ST, Yes Fairly soluble J. C + D 22 ≦2000 ppm  Good ST, Yes Fairly soluble K. A + E 21 ≦1000 ppm  Good ST, Yes Fairly soluble L. B + F 25 ≦500 ppm Good ST, Yes Fairly soluble M. A + G 23 ≦500 ppm Good ST, Yes Fairly soluble N. Perfluorobutyric acid + B 40 >1000 ppm  ST acceptable Encouraged O. Perfluoroacipic acid + B 55 <500 ppm ST too high No P. Perfluorosuberic acid + B 65 <100 ppm ST too high No ST: Surface Tension Later Experiments and those of Examples (1-4) using the surfactants in etchants were mainly focused on one of the surfactant compositions H, I, J, K, L, and M (of Table I).

Example 1

80 lbs. of an aqueous mixture comprised of 40% by weight of ammonium fluoride and 0.5% by weight of hydrofluoric acid (defined as BOE 100-1) was mixed with 500-ppm of surfactant “H” (a selected member of the claimed surfactant group as listed in Table I), by weight of the mixed etchant, and filtered through two 0.2-micron polyethersulfone (PES) filters. The surfactant mixture was not aggressively agitated, but circulated through filters runs for three days with interval samplings of approximately every four hours. The mean results are given in Table II below:

TABLE II Before After Meet Success Properties/Criteria Filtration Filtration Criteria (Yes/No) Surface Tension 18 38 Encouraged (dynes/cm²) Particulates (cts/ml) ≧1.0 micron >3,000 10 Yes ≧0.5 micron >10,000 33 Yes Foaming Insignificant Insignificant Yes The surface tension was found to increase following filtration. Data indicates the surfactants were removed during filtration, and failed to meet one of the success criteria. Another experiment was carried out to confirm with BOE 7-1 (see Example 2).

Example 2

200 ppm of surfactant “H” (Table I) were added into an aqueous mixture comprising of about 35% by weight of ammonium fluoride and about 6.3% by weight of hydrofluoric acid (defined as BOE 7-1), and without agitation, the mixture was circulated through two—0.2 μm filters (PES and Teflon or otherwise known as polytetrefluoroethylene or PTFE) and the results are given in Table III below:

TABLE III Before After Meet Success Properties/Criteria Filtration Filtration Criteria (Yes/No) ST (dynes/cm²) 20 36 Encouraged PC ≧1.0 μm —  6 Yes ≧0.5 μm — 82 Yes Foam Insignificant Insignificant Yes

Results similar to those of Example 1 were seen, despite different blends, concentrations of ammonium fluoride and hydrofluoric acid and different sets of filters (1 PES+1 Teflon instead of 2 PES). At this point, it was unknown whether the surfactant(s) filtered out or was not fully solubilized within the etching solution. A mechanical rotating blade mixer was introduced into the small pilot scale reactor to ensure that the contents were fully dispersed and a homogenized. Meanwhile, additional 100 ppm of surfactant “H” was added into the reaction vessel (assuming a worst scenario indicating that all surfactant(s) would filter out or fully load the capacity of the filters). Table IV below indicates an improvement of surface tension aided with a mixer following filtration.

TABLE IV Meet Success Properties/Criteria After Filtration Criteria (Yes/No) ST (dynes/cm²) 21 Yes PC (cts/ml) ≧1.0 μm  6 Yes ≧0.5 μm 54 Yes Foam Insignificant Yes Concentration of surfactant “H” in the pilot scale reactor is at 300 ppm, potentially in excess. Examples 3, 4, and 5 are an optimization of dosage and filter size variation.

Example 3

100 ppm surfactant “H” (Table I) was added into an aqueous mixture comprised of about 35% by weight of ammonium fluoride and about 6.3% by weight of hydrofluoric acid (defined as BOE 7-1), and with aid of agitation (mixer), the resulting solution was then filtered through one 0.2 μm PES filter for approximately 24 hours. Samples were taken for surface tension and particle count measurements prior to installing a 0.2 μm Teflon filter into a second filter housing in series. Results after PES filter and after teflon filter are illustrated in Table V below:

TABLE V After PES After Teflon Meet Success Properties/Criteria (1^(st) filter) (2^(nd) filter) Criteria (Yes/No) ST (dynes/cm²) 20 21  Yes PC ≧1.0 μm  3 1 Yes ≧0.5 μm 24 5 Yes Foam Insignificant Insignificant Yes

Changes in surface tension were insignificant on addition of another filter of same pore size and different material. Counts of sub-micron particulates decreased and indicated the surfactant(s) of the invention is filterable (particulate reduction while maintaining surface tension) with both PES and Teflon 0.2 μm filters.

Another conclusion from this example is that surfactant of the invention at 100 ppm concentration performs as well as 300 ppm in Example 2. Examples 4 and 5 are dosage optimization experiments with smaller filter size.

Example 4

A single 0.1 μm PES filter was used. Increments of 10 ppm surfactant “H” were added into an aqueous mixture comprised of approximately 35% by weight of ammonium fluoride and about 6.3% by weight of hydrofluoric acid (defined as BOE 7-1) until surface tension reached around surface tension of the 100 ppm as in Example 2. The mixer was operated for approximately five minutes after each addition. The critical point was established at 50 ppm. The results are given in

TABLE VI 50 ppm 50 ppm Meet Success Properties/Criteria Before Filtration After Filtration Criteria (Yes/No) ST (dynes/cm²) 20 21  Yes PC ≧1.0 μm 180 3 Yes ≧0.5 μm 1299 8 Yes Foam Insignificant Insignificant Yes

Experiment 4 was repeated to confirm the dosage by adding a single injection equivalent to 50 ppm surfactant “H” into BOE 7-1, followed by 5 minutes agitation with the mixer, and circulating through one 0.2 μm Teflon filter. The results are listed in Table VII.

TABLE VII 50 ppm Properties/Criteria After Filtration Status ST (dynes/cm²) 21 Pass PC (cts/ml) ≧1.0 μm  2 Pass ≧0.5 μm 11 Pass Foam Insignificant Pass Examples 1 to 4, specifically worked with the surfactant “H” (a selected member of the claimed surfactant group as listed in Table I), the pair of perfluorooctanoic acid and cycloheptyl amine. The study proceeded to investigate various homology pairs to determine whether similar results would be obtained in Example 5.

Example 5

Surfactant pair for this experiment consisted of perfluoroheptanoic acid and cycloheptylamine, surfactant “K” (a selected member of the claimed surfactant group as listed in Table I). Identical settings as other examples (reactor, temperature, mixer), and a single 0.1 μm PES filter were employed. 50 ppm of the surfactant pair was added into BOE 7-1. The results are displayed in Table VIII.

TABLE VIII Properties/Criteria Before Filtration After Filtration Status ST (dynes/cm²) 18 20 Pass PC ≧1.0 μm 292  3 Pass ≧0.5 μm 1498 18 Pass Foam Insignificant Insignificant Pass

Example 6

In the pilot scale reactor, 50 ppm by weight of surfactant “H” (Table I) was added into 60 lbs. of an aqueous mixture comprised of approximately 39.5% by weight of ammonium fluoride and about 1.1% by weight of hydrofluoric acid (defined as BOE 50-1), and with aid of a mixer, the blend was filtered through one 0.2 μm PES filter. Measurements of surface tension and particulates after filtration are in set forth in Table IX.

TABLE IX Properties/Criteria After Filtration Status ST (dynes/cm²) 21 Pass PC (cts/ml) ≧1.0 μm  9 Pass ≧0.5 μm 40 Pass Foam Insignificant Pass

Example 7

A manufacturing scale experiment was performed explicitly for product prequalification. A 3000 lbs. batch of an aqueous mixture comprised of approximately 34% by weight of ammonium fluoride and about 7.2% by weight of hydrofluoric acid (defined as BOE 6-1) with 50 ppm of surfactant “H” (same surfactant pair as in Examples 1-4) was produced under similar conditions as the pilot scale. The results are given in Table X below:

TABLE X Properties/Criteria Before Filtration After Filtration ST (dynes/cm²) 20 21 PC (cts/ml) ≧1.0 μm 576 1 ≧0.5 μm 10141 5 Foaming Insignificant Insignificant

Example 8

As in Example 7, another 3000 lbs. batch was produced and repeated 7 months after to confirm initial results. The data is shown in Table XI.

TABLE XI Properties/Criteria After Filtration ST (dynes/cm²) 20 PC (cts/ml) ≧1.0 μm Not available ≧0.5 μm Not available

Example 9

Another manufacturing scale experiment was performed explicitly for product pre-qualification under identical settings and conditions as the pilot scale and production batches in Examples 6 and 7. In this case, however, 50 ppm by weight of surfactant “H” was blended into a 3000 lbs. batch of an aqueous mixture comprised of approximately 17% by weight of ammonium fluoride and 0.15% by weight of hydrofluoric acid (defined as BOE 50). The final results are shown in Table XII.

TABLE XII Properties/Criteria After Filtration ST (dynes/cm²) 16 PC (cts/ml) ≧1.0 μm 36 ≧0.5 μm Not available

Example 10

A 60 lbs. aqueous mixture comprised of approximately 39.5% by weight of ammonium fluoride, about 1% by weight of phosphoric acid (defined as Blend B ammonium fluoride/phosphoric acid), and 10 ppm by weight of surfactant “H” were added. The blend was agitated with the aid of a mixer, and circulated through a 3□m polypropylene filter for 1 hour. Surface tension and particulates of the Blend B (ammonium fluoride/phosphoric acid) were measured before and after filtration as shown in Table XIII below:

TABLE XIII Properties/Criteria Before Filtration After Filtration ST (dynes/cm²) 24.6 24.6 PC (cts/ml) ≧1.0 μm 210 1 ≧0.5 μm 1695 6 Foaming Insignificant Insignificant

Example 11

In this run, surfactant “H” was tested with an aqueous solution of mixed etchants consisting of about 85% by weight of sulfuric acid, about 5% by weight of nitric acid, and about 1.5% by weight hydrofluoric acid. 100 ppm (Sample 1) and 200 ppm (Sample 2) by weight of surfactant “H” were mixed into two separate samples of FS Etch. The surface tension of both unfiltered samples was measured 1 hour upon batch completion and after 15 days of storage. The results are displayed in Table XIV.

TABLE XIV Surface Tension Surface Tension (dynes/cm2) (dynes/cm2) After 1 hr. After 15 days Sample 1 29 41 Sample 2 37 37

Surface tension of Sample 1 appears to increase over a period of time while at higher concentration of surfactant, Sample 2 shows higher surface tension 1 hour after addition of surfactant but appears stable after 15 days. In addition, some floating particulate matter was found on both samples immediately following mixing. However, the floating particulate matter decreases over the period of storage. Nevertheless, the results were encouraging and warranted further investigation.

Example 12

Stability Tests: Shelf life of filtered samples stored at room temperature (25° C.) were studied for the following stability evaluation of surfactant “H” (Table I) from Example 3 (BOE 7-1 with 100 ppm Surfactant), Example 4 (BOE 7-1 with 50 ppm surfactant), Example 6 (BOE 50-1 with 50 ppm surfactant), Example 9 (BOE 50-1 with 50 ppm of surfactant), and Example 10 (Blend B-ammonium fluoride/phosphoric acid with 10 ppm Surfactant). Results are given in Table XV wherein composition of etchants in percentage by weight are referenced.

TABLE XV Surface Surface Tension at Tension Retained Ammonium HF Storage Time of after Storage Samples Fluoride H3PO4* Surfactant Period Making Period From (%) (%) “H” (ppm) (Days) (dynes/cm²) (dynes/cm²) Example 3 35 6.3 100 30 21 22 Example 4 35 6.3 50 30 21 23 Example 6 39.5 1   50 120 21 21.5 Example 9 17  0.15 50 90 16 16.5 Example 39.5 1*  10 150 24.6 25.1 10 *In example 10, phosphoric acid is used in place of hydrofluoric acid.

Insignificant changes of surface tension were noted over time for the etchants listed in Table XV. A difference of 1-2 dyne/cm² is likely a measurement error or an influence of air bubbles in solution that interfere with surface tension measurements.

Example 13

Additional measurements of surface tension at 25° C. were carried out on unfiltered aqueous etchants of (1) 40% by weight ammonium fluoride, and (2) 9.2% by weight of hydrofluoric acid containing 100 ppm by weight of surfactant “H” (Table I). The results are indicated in Table XVI.

TABLE XVI Surface Tension Samples (dynes/cm²)  40% Ammonium Fluoride (Aqueous) 21 9.2% Hydrofluoric Acid (Aqueous) 31

Although the present invention has been described in terms of specific embodiments and, in particular, to the effectiveness of the surfactants of the invention when used in etchants, the invention is not to be so limited. Various changes can be made to the compositions used in formulating the surfactants and the application thereof in other filterable solutions in which the retention of surfactant effectiveness is desired. Thus the invention is only to be limited by the scope of the appended claims. 

1. An aqueous soluble surfactant comprising: (i) cyclic alkylamine of formula C_(x)H_(2x+1)N or (CH₂)_(x−1)CH NH₂ wherein x is an integer of 5 to 8; (ii) a linear perfluorocarboxylic acid of the formula C_(n)F_(2n−1)O₂H or C_(n−1)F_(2n−1)COOH wherein n is an integer of 4 to 11 and yields a perfluoroamide of the formula C_(n−1)F_(2n−1)CO NHCH(CH₂)_(x−1) wherein n=4 to 11 and x=5 to 8 when reacted with the cyclic alkylamine and (iii) an aliphatic alcohol of the formula C_(n)H_(2n+2)O, or C_(n)H_(2n+1)OH, wherein n is an integer of 1 to
 5. 2. The soluble surfactant of claims 1 wherein “(ii)” is an aqueous solution comprise of a blend of a cyclic alkylamine, perfluorocarboxylic acid and aliphatic alcohol and wherein the composition comprises at least 1% by weight of the cyclic alkylamine of the formula (CH₂)_(x−1)CHNH₂, at least 1% by weight of the Perfluorocarboxylic acid of the formula C_(n−1) F_(2n−1)COOH, and at least 10% by weight of the aliphatic alcohol of the formula C_(n)H_(2n+1)OH.
 3. The aqueous soluble surfactant of claim 1, wherein “ii” comprises about 10 ppm to about 500 ppm, of a combined quantity of cyclic alkylamine of the formula (CH₂)_(x−1)CHNH₂ and the perfluorocarboxylic acid of the formula C_(n−1)F_(2n−1)COOH, based on the weight of the etchant.
 4. The aqueous soluble surfactant of claim 1 wherein the cyclic alkylamine (i) is a member selected from the group consisting of cyclopentylamine, cycloheptylamine, and cyclooctylamine.
 5. The aqueous soluble surfactant of claim 1 wherein the linear perfluorocarboxylic acid (ii) of the formula C_(n−1)F_(2n−1)COOH is a member selected from the group consisting of tridecafluoroheptanoic acid (perfluoroheptanoic acid), pentadecafluorooctanoic acid (perfluorooctanoic acid), heptafluorobutyric acid (perfluorobutanoic acid), and heptadecafluorononanoic acid (perfluorononanoic acid).
 6. The aqueous soluble surfactant of claim 1 wherein the alcohol (iii) of the formula C_(n)H_(2n+1)OH is a member selected from the group consisting of 2-propanol, 1-propanol, ethanol, methanol, and 1-butanol. 